The reaction scheme, proposed by Eschenmoser et al. to account for the observed stereospecificity of steroid biosynthesis, postulates non- classical ions that involve the D-ring. To provide chemical evidence for the existence of such structures, investigations are proposed to explore whether the various rearrangements leading to uranediol and related structures can be accounted for by open cations differing at most in the position of the counterion, or whether bridged ions have to be invoked. The proposed work involves a new and hopefully more efficient approach to 13 alpha-D-homo-steroids.